Gamma Irradiation of Hexafluorobenzene

Mixtures of hexafluorobenzene and benzene were irradiated in liquid phase by means of a Co⁶⁰ gamma source at 20° and at 218° C. Perfluoroheptane and various binary mixtures involving perfluoroheptane, hexafluorobenzene, benzene, and cyclohexane were also irradiated at 20° C. Hexafluorobenzene resembled benzene very closely in its behavior upon radiolysis. Generally the fluorocarbon-hydrocarbon mixtures evolved much more SiF₄ (indicating the formation of HF, which reacts with the glass vessel) than the pure fluorocarbon components. The polymer from hexafluorobenzene-benzene mixtures was probably rich in cyclohexadiene and cyclohexene units, resembling that from pure benzene, and its composition ratio exhibited a strong "alternating" tendency. The results are discussed in terms of free-radical and excited-state mechanisms. At 218° C hexafluorobenzene and also its mixtures with benzene showed qualitative differences from their behavior at 20° C, although the G values for SiF₄ and polymer remained moderate.